A cyanobiphenyl-based fluorescent ''lighting-up'' sensor for highly selective and sensitive recognition of Al3+: Theoretical, practical and bioimaging studies.

The recognition of toxic Al3+ in foods and biosystems has of great interest to researchers. Herein, a novel cyanobiphenyl-based chemosensor CATH (E)-N'-((4'-cyano-4-hydroxy-[1,1'-biphenyl]-3-yl)methylene)thiophene-2-carbohydrazide was fabricated and shown to recognize Al3+ in HEPES buffer:EtOH (90:10, v:v, pH = 7.4) by ''lighting-up'' fluorescence sensing. The CATH evidenced high sensitivity (LOD = 13.1 nM) and excellent selectivity to Al3+ over competing cations. The Job's plot, TOF-MS and theoretical computation studies were performed to probe the binding mechanism of Al3+ to CATH. Additionally; CATH was successfully utilized to practical applications and employed to recover of Al3+ from different food samples. More importantly, it was employed to intracellular Al3+ detection in living cells including THLE2 and HepG2.

Ultrasensitive detection of Cu2+: A cyanobiphenyl-based colorimetric and fluorescence chemosensor and its Smartphone and food sample applications.

A new cyanobiphenyl-based compound 4-hydroxy-3-(((4-(phenylamino)phenyl)imino)methyl)-[1,1-biphenyl]-4-carbonitrile (PEBP) for Cu2+ detection was fabricated and successfully characterized. PEBP was employed as a sensor for Cu2+ sensing and used as an extremely fast responsive colorimetric and ''ON/OFF'' fluorescent sensor in H2O:CH3CN (40:60, v/v). Highly selective fluorescence response of PEBP to Cu2+ yielded an excellently low detection limit of 20.4 nM. Binding stoichiometry for PEBP-Cu2+ was found to be 2:1 by Job's plot study, as well MALDI TOF-MS data, and the binding constant was computed as 0.62 × 102 M-1/2. The validation study was employed using analytical parameters and statistical tests. To understand the binding capability, density functional theory (DFT) study was performed. Smartphone and applications for different food and drinking water samples were successfully constructed for Cu2+ detection, and the findings revealed that PEBP could be easily employed for in-site Cu2+detection without sophisticated instrument.

A novel ratiometric fluorescent and colorimetric sensor based on a 1,8-naphthalimide derivative for nanomolar Cu2+ sensing: smartphone and food applications.

A novel 1,8-naphthalimide-based chemical sensor 3-((2-(2-butyl-1,3-dioxo-2,3-dihydro-1H-benzo[de]isoquinoline-6-yl)hydrazone-o)methyl)-4-hydroxy-[1,1-biphenyl]-4-carbonitrile (BUDIN) with ratiometric fluorescence behavior, as well as "naked-eye" response was developed for the sensitive and specific determination of Cu2+ at nanomolar levels. With the addition of different amounts of Cu2+, the emission of BUDIN varied continually, leading to colour changes from yellow to blue (λem = 532 nm to 462 nm) due to intra-ligand charge transfer (ILCT) and metal-ligand charge transfer (MCLT). BUDIN can detect Cu2+ quantitatively with a detection limit of 17 nM. Job's plot, MALDI TOF MS and TOF MS findings revealed that the binding stoichiometry of BUDIN and Cu2+ was 2 : 1. Furthermore, the theoretical computation data strongly supported the optical response of BUDIN toward Cu2+. Smartphone digital imaging studies proved that BUDIN can be utilized as an outstanding chemical sensor for the on-site detection of Cu2+ without the need for sophisticated equipment, with a detection limit of 17.8 µM. The findings also presented that BUDIN is a very effective chemosensor for Cu2+ in real food samples with quite a simple operation.

Propylimidazole Functionalized Coumarin Derivative as Dual Responsive Fluorescent Chemoprobe for Picric Acid and Fe3+ Recognition: DFT and Natural Spring Water Applications.

A propylimidazole functionalized coumarin derivative (IPC) was fabricated for the first time and applied as a dual responsive fluorescent chemoprobe for sensitive and selective recognition of picric acid (PA) and Fe3+. Strong fluorescence quenching phenomena of the IPC were observed in H2O/ACN (5/95, v/v) medium (λem=408 nm) upon the additions of Fe3+or PA. The fabricated dual responsive IPC offered good selectivity and sensitivity with the low limit of detection values (0.92 µM for PA and 0.22 µM for Fe3+) lower than the acceptable amounts of Fe3+ and PA by the international official authorities. The validation study for the chemoprobe IPC for PA and Fe3+ was also performed. The interaction phenomena of IPC with PA and Fe3+ based on the findings of a range of experiments were considered and DFT computations were done to verify their recognition mechanisms. The sensing phenomena of IPC towards PA (1:1) and Fe3+ (3:1) were confirmed by the MALDI TOF-MS, FT-IR, 1H-NMR titration and Job's methods. Furthermore, the compound IPC was effectively applied as a fluorescent sensor for Fe3+ and PA detection in real natural spring water samples.

A rapid diagnostic approach for gastric and colon cancers via Fourier transform mid-infrared spectroscopy coupled with chemometrics from paraffin-embedded tissues.

This paper describes the feasibility of Attenuated total reflection-Fourier transform mid-infrared (ATR-MIR) spectroscopy method coupled with chemometrics for the rapid diagnostic approach and screening spectral changes for gastric and colon cancers from paraffin-embedded tissues. A total number of 82 tissue samples were analyzed by a simple ATR-MIR method combined with PCA, HCA, SIMCA and LDA methodologies. Spectral analyses showed significant differences for the molecular contents particularly about the lipid, nucleic acid, protein and other biomolecules in the samples of gastric cancer (GC) and colon cancer (CC) groups from their control/healthy groups. Significant changes in the characteristic of these molecules were only observed for cancer groups based upon the increment in their biosynthesis, and they could be utilized as diagnostic spectral biomarkers. Under the optimum conditions, SIMCA provided excellent classification for diseased and control groups, with 5% significance level. As well, 97.75% of the studied tissue samples were correctly discriminated on the basis of their origin by LDA. Consequently, the findings of this study highlighted the rapid diagnosis of gastric and colon cancer cases from paraffin-embedded tissues via ATR-MIR spectroscopy complemented with chemometrics.

Fabrication and sensing properties of phenolphthalein based colorimetric and turn-on fluorogenic probe for CO32- detection and its living-cell imaging application.

Herein, an easy assembled colorimetric and ''turn-on'' fluorescent sensor (probe P4SC) based on phenolphthalein was developed for carbonate ion (CO32-) sensing in a mixture of EtOH/H2O (v/v, 80/20, pH = 7, Britton-Robinson buffer) media. The probe P4SC demonstrated high sensitive and selective monitoring toward CO32- over other competitive anions. Interaction of CO32- with the probe P4SC resulted in a significant increment in emission intensity at λem = 498 nm (λex = 384 nm) due to the strategy of blocking the photo induced electron transfer (PET) mechanism. 1H NMR titration and Job's methods, as well as the theoretical study were carried out to support the probable stoichiometry of the reaction (1:2) between P4SC and CO32-. The binding constant of the probe P4SC with CO32- was calculated as 2.56 × 1010 M-2. The probe P4SC providing rapid response time (~0.5 min) with a satisfactorily low detection limit (14.7 nM) may be useful as a valuable realistic sensor. The imaging studies on the liver cancer cells (HepG2) shows the great potential of the probe P4SC for the sensation of intracellular CO32- anions. Furthermore, the satisfactory recovery and RSD values obtained for water application confirming that the probe P4SC could be applied to sensing of CO32- ion.

A novel phenolphthalein-based fluorescent sensor for Al3+ sensing in drinking water and herbal tea samples.

In this study, 3,3-bis(4-hydroxy-3-((E)-((4-hydroxyphenyl)imino)methyl) phenyl)isobenzofuran-1(3H)-one (HMBP) was designed as a ''turn-on″ fluorogenic chemosensor to detect Al3+. Studies were performed in C2H5OH-HEPES (v/v, 9/1, pH 7.0) media at λem = 475 nm. The LOD value was found to be 0.113 µM. The stoichiometric ratio of HMBP-Al3+ was determined as 1:2 by Job's plot and ESI-MS as well as 1H NMR titration. The binding constant of chemosensor HMBP with Al3+ from the Benesi-Hildebrand equation was determined to be 1.21 × 108 M-1. The quantum (Φ) yields were obtained as 0.040 and 0.775 for the chemosensor HMBP and HMBP-Al3+, respectively. The response of the chemosensor HMBP towards Al3+ was attributed to the strategies of blocking the photo-induced electron transfer (PET) and CN isomerisation mechanisms. Finally, the sensing of the chemosensor HMBP for the determination of Al3+ in real food samples, drinking waters and herbal teas, were employed.

Investigation of Wheat Germ and Oil Characteristics with Regard to Different Stabilization Techniques.

RESEARCH BACKGROUND: Utilization of wheat germ and wheat germ oil is limited due to high enzymatic activity and the presence of unsaturated fatty acids, which require stabilization techniques to overcome this problem. EXPERIMENTAL APPROACH: In this study, the effects of stabilization methods (dry convective oven heating at 90 and 160 °C, microwave radiation at 180 and 360 W, and autoclave steaming) on both wheat germ and its oil were evaluated. RESULTS AND CONCLUSIONS: Steaming caused the most dramatic changes in lipoxygenase activity, free fatty acid content, DPPH radical scavenging activity, and mass fractions of tocopherols and tocotrienols. Lower peroxide values were measured in the oil samples treated with convectional heating (160 °C) and steaming at temperatures above 100 °C. However, p-anisidine values of samples treated at higher temperatures were considerably greater than those of samples stabilized at lower temperatures. Oven heating at 160 °C was also one of the most effective treatments, after steaming, for the inactivation of lipoxygenase. Steaming significantly reduced mass fraction of total tocopherols, which was directly associated with the greater loss of ß-tocopherol content. On the contrary, γ- and δ-tocopherol and tocotrienol homologues were abundant with higher amounts in steamed samples. α-Tocopherol and γ-tocotrienol were the most resistant isomers to stabilization processes. NOVELTY AND SCIENTIFIC CONTRIBUTION: This study shows that the high temperature oven heating method, which is widely used in the industry for thermal stabilization of wheat germ, does not provide an advantage in oxidative stability compared to steaming and microwave applications. Steaming delayed oxidation in the germ, while further inhibiting lipoxygenase activity. Moreover, tocotrienols were more conservable. In industrial application, low-power microwave (180 instead of 360 W) and oven heating at lower temperature (90 instead of 160 °C) would be preferable.

Fluorescence "Turn On-Off" Sensing of Copper (II) Ions Utilizing Coumarin-Based Chemosensor: Experimental Study, Theoretical Calculation, Mineral and Drinking Water Analysis.

Herein, we report the preparation of a fluorescent sensor based on coumarin derivative for copper (II) ion sensing in CH3CN/HEPES media. 6,7-dihydroxy-3-(4-(trifluoro)methylphenyl)coumarin (HMAC) sensor was fabricated and analyzed by spectroscopic techniques. The sensor demonstrates "turn on-off" fluorescence quenching in the presence of copper (II) ions at 458 nm. A clear complex between the chemosensor HMAC and copper (II) ions was characterized by ESI-MS as well as the Job's method. Also, the limit of detection (LOD, 3σ/k) value was determined as 24.5 nM in CH3CN/HEPES (95/5, v/v) buffer media (pH = 7.0). This value is lower than the admissible level of copper (II) ions in drinking water (maximum 31.5 µM) reported by EU Water Framework Directive (WFD) and World Health Organization (WHO) guidelines. The theoretical calculations (density functional theory, DFT) have been performed for the geometric optimized structures. As a final stage, real sample analyses have successfully been performed by using HMAC, as well as ICP-OES method. The relative standard deviation for copper (II) in mineral and drinking water samples has been determined to be below 0.15% and recovery values are in the range of 95.48-109.20%.

Fluorescent sensing platform for low-cost detection of Cu2+ by coumarin derivative: DFT calculation and practical application in herbal and black tea samples.

A fluorogenic probe based on a coumarin-derivative for Cu2+ sensing in CH3CN/H2O media (v/v, 95/5, 5.0 µM) was developed and applied in real samples. 3-(4-chlorophenyl)-6,7-dihydroxy-coumarin (MCPC) probe was obtained by synthetic methodologies and identified by spectral techniques. The probe MCPC showed remarkable changes with a "turn-off" fluorogenic sensing approach for the monitoring of Cu2+ at 456 nm under an excitation wavelength of 366 nm. The response time of the probe MCPC was founded as only 1 min. The detection limit of the probe MCPC was recorded to be 1.47 nM. The binding constant and possible stoichiometric ratio (1:1) values were determined by Benesi-Hildebrand and Job's plot systems, respectively. The mechanism of the probe MCPC with Cu2+ was further confirmed by ESI-MS and FT-IR analyses, as well as supported by theoretical calculations. Furthermore, the probe MCPC was successfully employed for the practical applications to sense Cu2+ in different herbal and black tea samples. The proposed sensing method was also verified by ICP-OES method.

Methods for one- and two-dimensional gas chromatography with flame ionization detection for identification of Mycobacterium tuberculosis in sputum.

Two simplified methods based on manual thermally-assisted hydrolysis and methylation (THM) GC and GC × GC with flame ionization detection (FID) were developed for the detection of mycobacteria and Mycobacterium tuberculosis (MTB) in sputum. A central composite design was employed to optimize the THM derivatization conditions. For the detection of MTB the known mycobacterial markers tuberculostearic acid (TBSA) and hexacosanoic acid (C26), as well as three MTB specific markers, the mycocerosates, were evaluated. We found that the optimum conditions for THM release of TBSA and C26 differ from those for maximum release of the mycocerosates. Higher reagent volumes, higher temperatures and longer incubation increase the mycocerosates yield. Application of these conditions unfortunately resulted in unacceptable safety hazards. A GC × GC-FID method was developed that allowed accurate detection of mycocerosates even at poor conversion yields of the derivatization reaction. Using spiked sputum samples from non-TB patients, the detection limit of the method based on TBSA and C26 was found to be comparable to that of microscopy, i.e. 104-105 bacteria/mL sputum. To validate the new test, we compared the results we found for fifteen sputum samples from patients from South Africa suspected of having tuberculosis with those of culture, the gold standard method. Based on the presence of TBSA and C26, all eight microscopy and culture positive samples, and even two microscopy negative but culture positive samples were positive by THM-GC-FID. All five microscopy and culture negative sputum samples were also negative for THM-GC-FID, giving a specificity of 100%. Using GC × GC-FID we could detect mycocerosates, the specific markers for MTB in seven out of ten MTB culture positive sputum samples. The five culture negative cases were also negative for mycocerosates in manual THM-GC × GC-FID giving again 100% specificity. The results obtained indicate that the new methods hold great potential for the early diagnosis of TB in developing countries.

Synchronous fluorescence spectroscopy combined with chemometrics for rapid assessment of cold-pressed grape seed oil adulteration: Qualitative and quantitative study.

This paper describes the feasibility of synchronous fluorescence (SyF) spectroscopy combined with multivariate data analysis for qualitative and quantitative determination of adulteration of cold pressed grape seed oil (GSO) with refined soybean oil (SBO). SyF spectroscopy data of oil samples were collected in the region of 250-800 nm at excitation-emission wavelength differences (∆λ) of 10, 20, 30, 40, 50, 60, 70 and 80 nm. Three different multivariate methods, namely principal component analysis (PCA), soft independent modeling of class analogies (SIMCA) and partial least square regression (PLSR) analysis were used for data analysis. To simulate the adulteration of cold pressed GSO with refined SBO, ninety-six adulterated samples were prepared at adulterant levels from 5% to 50%. HPLC-FLD method was used as reference in order to authenticate pure oils and binary oil mixtures. The SIMCA models provided an excellent classification for pure cold pressed GSO versus other vegetable oil samples, with a 95% significance level. The classification error rate of SyF spectroscopy for detecting SBO added to GSO was also better than 5%. PLSR calibration models constructed for the evaluation of GSO purity and for the adulterants SBOs were internally validated by the leave-one-out procedure (cross-validation) and their predictive ability was assessed by independent external validation sets. Under the optimum conditions, the plots of observed versus predicted values exhibited a good linearity (R2 > 0.99). The root mean square errors of calibration (RMSEC) and cross-validation (RMSECV) were in the range 0.55-4.46% and 2.14-5.35%, respectively. Excellent predicting capabilities were also obtained using an external validation set consisting of GSO adulterated with SBOs from different brands.

Application of multivariate chemometric techniques for simultaneous determination of five parameters of cottonseed oil by single bounce attenuated total reflectance Fourier transform infrared spectroscopy.

Single bounce attenuated total reflectance (SB-ATR) Fourier transform infrared (FTIR) spectroscopy in conjunction with chemometrics was used for accurate determination of free fatty acid (FFA), peroxide value (PV), iodine value (IV), conjugated diene (CD) and conjugated triene (CT) of cottonseed oil (CSO) during potato chips frying. Partial least square (PLS), stepwise multiple linear regression (SMLR), principal component regression (PCR) and simple Beer׳s law (SBL) were applied to develop the calibrations for simultaneous evaluation of five stated parameters of cottonseed oil (CSO) during frying of French frozen potato chips at 170°C. Good regression coefficients (R(2)) were achieved for FFA, PV, IV, CD and CT with value of >0.992 by PLS, SMLR, PCR, and SBL. Root mean square error of prediction (RMSEP) was found to be less than 1.95% for all determinations. Result of the study indicated that SB-ATR FTIR in combination with multivariate chemometrics could be used for accurate and simultaneous determination of different parameters during the frying process without using any toxic organic solvent.